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Inkjet Printing of Lanthanide-Organic Frameworks for Anti-Counterfeiting Applications Leonis Lourenço da Luz, Raquel Milani, Jorlandio Francisco Felix, Igor R. B. Ribeiro, Márcio Talhavini, Brenno A. D. Neto, Jaroslaw Chojnacki, Severino Alves, and Marcelo Oliveira Rodrigues ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 02 Nov 2015 Downloaded from http://pubs.acs.org on November 2, 2015

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ACS Applied Materials & Interfaces

Inkjet printing of Lanthanide-Organic Frameworks for Anti-Counterfeiting Applications Leonis L. Luz,a Raquel Milania, Jorlandio F. Felixb,c, Igor R. B. Ribeirob Márcio Talhavini,e Brenno A. D. Netod, Jaroslaw Chojnacki g, Marcelo O. Rodrigues,a,f*and Severino A. Júniora*

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a

Departamento de Química Fundamental, UFPE, 50670-901, Recife, PE, Brazil. Tel. +55 81 2126-7475; Fax: +55 81 2126-8442; b

Departamento de Física—Universidade Federal de Viçosa, 36570-900, Viçosa, Minas; Gerais, Brazil

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c

Universidade de Brasília, Instituto de Física, Núcleo de Física Aplicada, Brasília DF 70910-900, Brazil;

d

Laboratory of Medicinal and Technological Chemistry, University of Brasilia (IQ-UnB). Campus Universitario Darcy Ribeiro, CEP 70904970, P.O.Box 4478, Brasilia-DF, Brazil;

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e

Instituto Nacional de Criminalística – INC, Departamento de Polícia Federal – DPF, Laboratório de Criminalística. SAIS, quadra 07, lote 23, 70610-200, Brasíia, Brazil

f

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LIMA - Laboratório de Inorgânica e Materiais, Campus Universitário Darcy Ribeiro, CEP 70904970, P.O.Box 4478, Brasilia-DF, Brazil. g

Gdansk University of Technology, Department of Chemistry, G.Narutowicza 11/13, PL-80233, Gdansk, Poland

25 Abstract Photoluminescent Lanthanide-Organic Frameworks (Ln-MOFs) were printed onto plastic and paper foils with a conventional Inkjet printer. Ln-MOF inks were used to reproduce color images that can be only observed under a UV light irradiation. This approach opens up a new window to explore Ln-MOF materials in technological applications, such as optical devices (e.g. lab-on-a-chip), proof of authenticity for official documents.

Keywords. Lanthanides, Metal-Organic Frameworks, Inkjet print, Luminescence and Anti-Counterfeiting.

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•

INTRODUCTION

New functional materials associated with innovative fabrication procedures is fostering technological developments of more specialized and sophisticated devices.1,2 In the last few years, high-technological sectors have explored magnetic, optical, size and conducting properties of new 5

materials and a diversity of processing techniques for the production of integrated circuits, smart textile,3 batteries,4 solar cells,5 electroluminescent devices,6 sensors7,8 and others. The most of manufacturing processes use subtractive patterning methods and deposition of the materials under high temperatures and ultra-vacuum conditions. Recent innovations in printing, roll-to-roll and coating processes became some alternatives for the fabrication of customizable devices onto various

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substrates.2,9,10

In this context, coordination polymers (CPs) and metal-organic frameworks (MOFs) emerged as a versatile class and subclass of hybrid materials, which have attracted tremendous attention due to their intriguing structures, topological aspects, and potential for technological applications.11,12 Thousands of CPs and MOFs structures were systematically produced in the last 15

two decades and the net result was a considerable progress regarding controlled syntheses and production of specific functionalities and tunable properties. MOFs and CPs have been explored in important fields such as biomedicine,13 sensing,14 gas storage,15 separation,16 adsorption,17,18 drug delivery,19 forensic science20 and catalysis.21 MOFs are also regarded as an excellent platform for the production of light emissive materials, because they offer a well-defined chemical environment

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for emitter centers and their hybrid character renders them a diversity of optical phenomenon uncommon in classical light-emitting materials.20,22-24 Among the plethora of luminescent CPs and MOFs already reported, those based on lanthanide ions, that is lanthanide-organic frameworks (LnMOFs), are the most promising type because they combine fairly interesting structures, thermodynamic stability with the well-known magnetic behavior and spectroscopic properties

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originated from the lanthanide ions.24,25


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Most of MOFs applications reported hitherto are limited to bulk materials because, similarly to zeolites, MOFs materials are insoluble in most of the solvents therefore hindering the preparation of thin films form or anchoring in substrates.26,27 More recently, several research groups have achieved significant progress in deposition of MOFs onto substrates.28,29 For instance, Férey’s 5

group has produced a flexible thin film of MIL- 89 ( Fe3OCl(O2C—C4H4—CO2), where O2C— C4H4—CO2 is the muconate dicarboxylate ligand) by dip-coating on silica substrate with high optical quality.30 Production of well-oriented thin films based on surface-attached MOF materials (SURMOFs) has gained significant importance for integrated device construction.31 Electrospinning has also demonstrated to be valuable for encapsulation MOFs materials and production of one-

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dimensional nanofibers.32 Despite the aforementioned potentialities, MOFs-based miniaturized devices are extremely scarce, since the control of the crystal size, position and orientation on substrates remains a complex and hard task.33 Innovative processing methods for MOFs and CPs may therefore be considered as the ultimate challenge for enhancing their high-technological industrial applicability. In this perspective, Falcaro and coworkers have developed several

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deposition protocols for MOF materials based on soft lithography.29,33 Alternatively, Terfort and coworkers developed a synthetic procedure that have enabled HKUST-1 ([Cu2(btc)2], btc= 1,3,5 benzenetricarboxylate) and [Zn2(adc)2(dabco)2] (adc and dabco are 9,10-anthracenedicarboxylate and 1,4-diazabicyclo[2,2,2]octane, respectively) to be explored as a high stable “ink”.34 These MOFs Inkjet printing is an attractive and advantage methodology over conventional approaches,

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such as rapid processing rates, deposition in large areas without contamination, generation of minimal residues and wide processability of computer-aided design (CAD) information.34 Inkjet printing

method has been used to print macromolecules,35,36 nanoparticles,37 and therapeutic

drugs.38 Also, it is used for the fabrication of flexible displays,39 solar cells,40,41 as catalysts,42 explosive sensor,43 transistors,44 data storage45 and medical devices.46,47 Most recently, as a bid to 25

enhance the security of documents and product authenticity and traceability, inkjet printing of luminescent molecules and inorganic nanocrystals emerged as a low cost and customizable anti-



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counterfeit technology.48 Based on this new conception for MOFs and CPs processing, we report herein an effective procedure for the fabrication of “inks” based on Ln-MOFs and their deposition onto flexible substrates with an off-the-shelf inkjet printer. This straightforward method permits to produce photoluminescent inks for invisible security labelling/encoding and supported catalysts as 5

will be disclosed in due course.

• RESULTS AND DISCUSSION In this work, we have focused on the deposition of the [Ln2(Mell).6H2O] as inks, where Ln = Eu3+, Tb3+, Gd+3 or Nd3+ and Mell = mellitate, namely respectively as R-MOF , G-MOF , BMOF and NIR-MOF in accordance with previous reports.25 One of the most interesting features of 10

[Ln2(Mell).6H2O] is the easy of fabrication of high photoluminescent crystals at room temperature. Recently, [Ln2(Mell).6H2O] were successfully used as a platform for production of white-light emitting materials through layer-by-layer deposition of red, green and blue emitters.25 The synthesis of [Ln2(Mell).6H2O] materials were modified with the propose of rapid production of crystals. In the optimized synthetic approach, a mixture of mellitic acid (0.5 mmol), [Ln(NO3)3.6H2O] (0.5

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mmol) and H2O (5.0 mL) were kept under constant magnetic stirring during 5 minutes and transferred to a 15 mL falcon tube. Rapid crystal nucleation was triggered by a slow addition of 1.5 mL (30% in volume) of organic solvents, such as ethanol, propanol or methanol. Microcrystal were obtained in 53 % yields. The slow diffusions of the precipitant agents permit to obtain large and well-formed crystals suitable for single-crystal X-ray diffraction after only 5 minutes. The alcohol

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molecules added in the reaction mixture play an important role in Ln-MOFs crystallization, since they might completely or partially replace the solvent precursor around the building blocks, which induce a rapid crystal nucleation, as described elsewhere.49 The single-crystal and powder X-rays diffraction analysis reveals that R-, G- and B-MOFs materials, herein reported, are indeed isostructural and identical to those previously reported.25,50,51 Figures S1 e S2 (in the supporting

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information) depict the Ln-MOF structure along of b axis and their diffraction powder patterns.


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Depositions of patterned Ln-MOF materials onto flexible substrates (transparency PET films 3M and paper sheets) were carried out with an unmodified mechanical type print head Inkjet Printer Cannon Pixma MP495 (Canon Inc. Japan). The ink solutions presented values of kinematic viscosities of 0.83 and 0.74 mm2.s-1 at 25 and 40 ºC which are similar to that used in conventional 5

inks. The transparency PET foils were used as-made or after washed 3 times with absolute ethanol (treated PET), aiming at removing the coated gel films that increase the adhesion of the inks. The removal of the coated gel was monitored via contact angle experiments and infrared spectroscopy. When the aqueous inks dropped on the pieces of the as-made and treated transparency foils, they have shown significant variations on their respective contact angles. As-made PET foils present a

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gradual reduction of 14.1 degrees (54.6 to 40.5º) in 300 seconds, while the contact angle for treated PET foils remains at 62.5º during the experiments. The higher contact angle presented by treated plastic sheet indicates that the hydrophilic gel was completely removed from its surface. These results are corroborated by the IR spectra acquired for the PET substrates. The aqueous Ln-MOF “ink” solutions (3.0 mL) were placed in the color inkjet cartridge (10.00 mL), and a 90% ethanolic

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solution (precipitant agent) was added in the black cartridge. A resolution of 1200 dpi in a single printing cycle were used to deposit the Ln-MOFs inks, and following the printed substrates dried for 5 minutes at room temperature. It is important to note that the small ink volume (2-10 pL) allows a fast drying of the ink solvent, furthermore, rapid crystal nucleation permits to produce patterned photoluminescent Ln-MOFs without the multiply “printing-drying” cycles, as described

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in previous reports. Scheme 1 illustrates the processing used to print photoluminescent Ln-MOFs.



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Scheme 1. Schematic representation to inkjet print of Ln-MOFs.

R- and G-MOF were printed individually onto polyethylene terephthalate (PET) foils to 5

avoid the interference of superposition of the ink halftone dots. Photoluminescence measurements were performed for Ln-MOFs materials patterned onto treated (washed 3 times with absolute ethanol) and untreated transparency films and compared with those of Ln-MOFs crystals. Figure 1 presents the emission spectra acquired at room temperature upon excitation at 254 nm for Ln-MOFs (a) and (b) and the printed designed patterns under ultraviolet irradiation (c) and (d). The emission

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spectra display narrow bands characteristic of the Eu3+ 5D0→7FJ and Tb3+ 5D4→7FJ transitions.52 The relative intensities and the number of Stark components are dependent upon the extent in which the (2J+1) degeneracy is removed by the symmetry of the first coordination sphere, thus, they can be used as probe of symmetry sites in europium-based compounds.52 The as-prepared and the printed Eu-MOFs onto treated substrate (Figure 1(a)) show an identical spectral profiles a

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consistent with no structural alterations or significant defects caused by rapid crystallization, as previously described for other MOFs materials. In contrast, the emission in Ln-MOFs materials deposited onto untreated transparencies exhibit broader emission lines, which may be justified by structural alteration induced by the coated gel film. Table S1 collects the spectroscopic data for the Ln-MOF materials reported herein.


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Figure 1. (a) and (b): Emission spectra of R- and G-MOF inks. Solid red and green lines represents the emission spectra of the R- and G-MOF crystals, whereas, solid black and blue lines denote the emission spectra of R- and GMOF inks deposited onto treated and as-made transparency PET foils (c) and (d): LnMOF inks deposited onto treated

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transparency PET substrates under UV light irradiation (λexc= 254 nm).

The inkjet printing of Ln-MOFs were successfully tested not only in plastic substrates, but also on several types of papers. Figures 2 shows the theoretical and experimental color tones, emission spectra upon excitation at 254 nm, spectral barcode and CAD images designed using simultaneously Eu- and Tb-MOFs inks.



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Figure 2. (a): Theoretical/Experimental RGB and CMYK color models and photoluminescent color tones (λexc= 254 nm) designed in proportional ratio of R- and G-MOF; (b): Emission spectra of color gradients produced by R- and GMOF; (c) Luminescent barcode patterns obtained by integrated intensities of the Eu3+ and Tb3+ transitions; (d) and (e):

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Xylograph of the “Os Retirantes” (public image) and Ln-MOF structure printed onto vegetal paper sheets under UV light irradiation . (f) and (g): Fragment of the Hamlet by William Shakespeare printed onto vegetal paper codified with Ln-MOF under white and UV light irradiation, respectively. Aiming at showing a perfect adhesion of the Ln-MOF onto the paper, first the paper was crumpled and then irradiated it with white and UV light (λexc= 254 nm).

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The color gradient, exhibited in Figure 2(a), were designed by using R- and G-MOFs inks ratios with RGB/CMYK values: 1: 138, 239, 174/ 29%, 100%, 29%, 29%; 2: 176, 236, 174/ 65%, 100%, 29%, 29%; ACS Paragon Plus Environment

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3: 255, 255, 172/100%, 100%, 29%, 29%; 4: 255, 231, 172/100%, 65%, 29%, 29%; 5: 255, 157, 131/ 100%, 29%, 29%, 29%. The photoluminescent inks were systematically deposited by halftone technique, which 5

permits to produce color gradient effect by precise control of the size, distance and superposition of the Ln-MOFs “ink” dots. The addictive luminescent colors obtained by superposition of the R- and G-MOF inks dots demonstrate a good reproducibility when compared with the theoretical ones. Recent works have reported that the deposition of photoluminescent inks via halftone method does not cause color quenching.53 It can be justified by the emitter centers that are inserted in distinct

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host domains.25,54 The emission spectra exhibited in Figure 2(b) presented simultaneously emission transitions typical of Tb3+ and Eu3+ ion whose the amplitude have presented a dependence with each ink dots quantities. Interestingly, luminescence investigations also demonstrate the different quantities of R- and G-MOFs ink dots onto substrate surfaces can provide singular and discernible spectroscopic barcodes (Figure 2(c)). Figures 2 (d) and (e) illustrate the Ln-MOFs patterns

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deposited onto the paper substrate, demonstrating that the inkjet printing technique with Ln-MOF inks allows to create complex hidden images useful for counterfeit prevention. A Hamlet's fragment of William Shakespeare was overprinted in the same area of the “inks” with a conventional monochromatic laser printer (HP LaserJet 1022), Figures 2 (f) and (g), in order to investigate the thermal stability and adherence of the patterned Ln-MOFs. The MOF printed regions present the

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same luminescence uniformity presented before the abrasive overprinting and crumpling processes. In Figure 3 and 4 are available a sequence of images acquired for peel adhesion and abrasion resistance tests. Figure 5 shows the images of the G-MOF deposited onto vegetal paper substrates upon thermal treatment of 30 minutes in different temperatures.



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Figure 3. Sequence of images of tape peel adhesion test acquired for the substrates under white and UV light irradiation (λexc= 254 nm). (a): as-made transparency PET foils; (b) treated transparency PET foils; (c): paper sheet.


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Figure 4. Sequence of images of abrasion test performed with a rubber eraser for the substrates under white and UV light irradiation. (λexc= 254 nm). (a): as-made transparency PET foils; (b) treated transparency PET foils; (c): vegetal paper.

5 Figure 5. G-MOF printed onto vegetal paper substrates under white (a) and UV light (b) irradiation upon thermal treatment of 30 minutes at 60, 100, 150 and 200°C.



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From the image sequences presented in Figures 3 and 4, it is evident that the Ln-MOF inks remains adhered onto the surface of the as-made transparency PET and vegetal paper sheets even after the mechanical stress caused by tape peeling and rubber friction, whereas they were easily removed from the treated transparency PET sheet. These results imply that the hydrophilic 5

surface of the as-made PET and vegetal paper play important role in adhesion of the Ln-MOF crystals. The visual results of the thermal treatment exposed in Figure 5 has shown that even after 30 minutes under high temperatures the G-MOF ink printed onto paper substrate presented a good stability, which is consistent with TGA curves exhibited in Figure 8S. These results indicate that the Ln-MOF inks are promising for codification of documents and production of counterfeit items,

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since they have exhibited good stabilities and adhesion onto hydrophilic substrate surface even upon the exposition to stress caused by bending, peeling, abrasion, high temperatures of the fuser roller of laserjet printers (≈ 200 ºC)55 and thermal treatments for long times. The photoluminescent colors associated with singular spectral fingerprints make the LnMOFs inks also highly attractive for the exploration as security elements in anti-counterfeit

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technologies. The emission spectra of B-MOF and NIR-MOF, displayed in Figure 6, show a board band at blue region typical of ligand centered emission. NIR-MOF still exhibits two emission band centered at 1070 and 1350 nm which can be attributed to 4F3/2→4I11/2 and 4F3/2→4I13/2 transitions of Nd3+ ions. NIR emission bands cannot be detected by the naked eyes, hence, these signals can used as proof of authenticity because they are only identified spectroscopically. These results could make

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NIR-MOF inks potentially candidates for development of photoluminescent blue-NIR-emitting inks.


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Figure 6. (a) and (b): Photoluminescence spectra of B-MOF and NIR-MOF. The excitation spectra were acquired at room temperature while monitoring the emissions of B-MOF and NIR-MOF at 450 and 437nm; (c) Photoluminescence spectra of NIR-MOF. Excitation spectrum was obtained at room temperature while monitoring the

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transition 4F3/2→4I11/2 at 1070 nm.

In order evaluate the reproduction of invisible full color images R-, G- and NIR-MOF were placed in cyan, magenta and yellow partitions of a tri-color, respectively. In Figure 7 presents



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the emission spectra and theoretical/experimental photoluminescent color tones obtained under excitation at 254 nm for the superposed R-, G- and NIR-MOF inks. The spectra were acquired at room temperature upon excitation at 254 nm. The emission spectra, exhibited in Figure 7 (a), display broad bands centered at around 430 nm of the ligand emission of NIR-MOF. The narrow 5

band between 480 and 720 nm can be assigned to the 5D0→7FJ and 5D4→7FJ transitions of the Eu3+ and Tb3+ ions. In Figure 5 (b) show the emission lines of the Nd3+ cations in NIR region. The paper surface covered with R-, G- and NIR-MOF present a poor color reproducibility that can be justified by the low blue emission intensity of the NIR-MOF and irregular distributions of the microcrystals onto the substrate surfaces.

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Figure 7. (a) and (b): Emission spectra in visible and near infrared regions produced by superposition of the R-,G and NIR-MOF photoluminescent inks. (c) and (d): RGB (λexc= 254 nm) and CMYK color models designed in proportional ratio of the three luminescent inks. Note: (1)-(5) numbers were used to correlate the emission spectra and the colors produced.


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Figure 8. (a) and (b): SEM images of R-MOF printed onto treated, untreated PET foils. (c) and (d) SEM images of GMOF deposited on vegetal paper substrate. (e) and (f): AFM images of R-MOF printed on a treated transparent PET surface.

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SEM and AFM images of printed substrates in single-printing cycle are shown in Figure 7 (a)-(f). The SEM images obtained for plastic and paper substrates show the surface partially covered with Ln-MOFs microcrystals with a board size distributions (0.4-8.0 µm) after singleprinting cycles. Atomic force microscopy (AFM) in non-contact mode was used to obtain the topographic images recorded with a silicon tip (radius < 5 nm). The AFM images of Ln-MOFs

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printed on a treated transparent PET surface (Figures. 8 (e)) and on untreated transparent PET surface (Figures 8 (f)). The image shows that the G-MOFs crystal is homogeneous when printed on



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treated PET surface. On the other hand, when both R-MOFs and G-MOFs are printed on untreated PET surface, the MOFs crystals are embedded in the gel and the grains are more separated from each other. This effect could be related with broader emission lines shown in Figure 1(a) and 1(b).

• CONCLUSION 5

In summary, we have demonstrated a facile, low-cost and time-efficient strategy for the positioning of photoluminescent Ln-MOFs on flexible substrates (paper and plastic foils) by using a conventional commercially available inkjet printer. The spatial control over the positioning MOF and CPs is still a challenging task and this work furthers this amazing new technology. This work also opens up several possibilities to develop multifunctional miniaturized platforms based on Ln-

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MOF materials and technological applications, such as optical devices (e.g. lab-on-a-chip), proof of authenticity for official documents (forensic applications), sensing, and, as will be evaluated disclosed elsewhere, catalysts.

SUPPORTING INFORMATION AVAILABLE: Crystallographic information, FT-IR spectra of PET films and Ln-MOF materials, Contact angle experiments, TGA curves and photoluminescent 15

spectra This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding author footnote. * Prof. Dr. Marcelo O. Rodrigues, LIMA-Laboratório de Inorgânica e Materiais, Campus

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Universitário Darcy Ribeiro, CEP 70904970, P.O.Box 4478, Brasilia-DF, Brazil. Fax: (+) 55 (61) 32734149; Phone +55 61 3107-3898; E-mail: [email protected] * Prof. Dr. Severino A. Júnior, BSTR, Departamento de Química Fundamental, UFPE, 50670-901, Recife, PE, Brazil. Tel. +55 81 2126-7475; Fax: +55 81 2126-8442; E-mail: [email protected]

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Acknowledgments: The authors gratefully acknowledge CNPq (INCT/INAMI and RHINCT/INAMI), DPP-UNB. FAP-DF, FACEPE and CAPES for its financial support. We would like to thank Dr. Euzébio Skovroisky.


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